US4529807A - Furfuryl esters and resins - Google Patents

Furfuryl esters and resins Download PDF

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US4529807A
US4529807A US06/574,664 US57466484A US4529807A US 4529807 A US4529807 A US 4529807A US 57466484 A US57466484 A US 57466484A US 4529807 A US4529807 A US 4529807A
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furfuryl
ester
esters
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sand
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US06/574,664
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Wayne D. Woodson
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Ashland Inc
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CL Industries Inc USA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings

Definitions

  • This invention relates to new and useful acid-curing resin compositions for use in the formation of sand cores and molds for foundry operations and to new di-esters of lower aliphatic dibasic acids.
  • sand is coated with resin binders and formed into molds and cores for the production of precision castings.
  • a wide variety of techniques have been developed for the manufacture of sand cores and molds. These involve the hot box technique for mold and core formation; the shell method; the "No-Bake", and the cold-box technique.
  • sand molds and cores are formed by heating a mixture of sand and a thermosetting resin at a temperature of about 300°-600° F. in contact with patterns which produce the desired shape for the mold or core.
  • the resin is polymerized and a core or mold is formed. Procedures of this type are described in Dunn U.S. Pat. No. 3,059,297 and Brown U.S. pat. No. 3,020,609.
  • a particular disadvantage of the hot box and shell methods is the necessity for heating the pattern boxes to 300°-600° F. to polymerize and cure the resin binder. This involves considerable expense and is generally a high cost technique.
  • the cold box techniques for core and mold formation involve the use of sand mixed or coated with resins which may be cured at room temperature by acid or base catalysis. Acidic or basic catalysts have been used in liquid, solid or gaseous form. Typical cold box processes are shown in Blaies U.S. Pat. No. 3,008,205; Dunn U.S. Pat. No. 3,059,297; Peters U.S. Pat. No. 3,108,340; Kottke U.S. Pat. No. 3,145,438; Brown U.S. Pat. No. 3,184,814; Robins U.S. Pat. No. 3,639,654; Australian Pat. No. 453,160 and British Pat. No. 1,225,984.
  • Dannenberg U.S. Pat. No. 2,650,211 discloses polymers including dibasic acids as precursors.
  • Treat U.S. Pat. No. 2,999,829 discloses the copolymerization of furfuryl alcohol and maleic anhydride in the prepatatio of foundry cores.
  • Guyer U.S. Pat. No. 3,404,118 discloses the use of furfuryl glycidyl ether in molding resins.
  • Adkins U.S. Pat. No. 3,725,333 discloses the preparation of foundry molds, etc. using phenolic resins modified with furfuryl alcohol.
  • Laitar U.S. Pat. No. 4,051,301 discloses resins for sand cores or molds by incorporating furan into a furfuryl alcohol-modified phenolic resin prepolymer.
  • British Pat. Nos. 626,763 and 992,345 disclose the use of glyceryl esters and other esters of aliphatic dibasic acids in condensation polymers.
  • the bis(tetrahydrofurfuryl) ester of adipic acid is known but does not undergo condensation type polymerization.
  • Another object of the invention is to provide resin compositions having the properties and desires characteristics of furfuryl alcohol-containing resins without the problems of short bench life and working time.
  • Another object of the invention is to provide a novel class of compounds which is useful in modifying condensation-type resins.
  • novel resin compositions comprising acid-curable, condensation-type resins, particularly phenolic resin prepolymers and urea-formaldehyde and/or furfuryl alcohol-formaldehyde modified phenolic resin prepolymers admixed with a dibasic acid di-ester of the composition
  • n is from 1 to 8
  • R 1 is furfuryl
  • R 2 is furfuryl or methyl.
  • the di-esters are preferably added in the amount of 5-35%, by weight of total composition. These compositions are particularly useful in the preparation of sand cores and molds for foundry use which have improved strength and hardness.
  • R 1 is furfuryl
  • R 2 is furfuryl or methyl
  • These di-esters are oily liquids having high boiling points and are particularly useful as resin modifiers, diluents and plasticizers. These di-esters are produced by the sodium-catalyzed transesterification reaction of furfuryl alcohol with the liquid dimethyl esters of the C 3 -C 10 linear aliphatic dibasic acids at temperatures of about 214°-240° F.
  • the difurfuryl esters and mixed methyl-furfuryl esters of aliphatic dibasic acids are prepared by a sodium-catalyzed transesterification of the corresponding dimethyl esters.
  • Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F.
  • Dimethyl glutarate is a very high boiling liquid, b.p. 417° F.
  • Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F.
  • Dimethyl succinate is a very high boiling liquid, b.p. 385° F.
  • Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F.
  • Dimethyl adipate is a very high boiling liquid, b.p. 235° F., at 13 mm.
  • Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F.
  • Dimethyl malonate is a very high boiling liquid, b.p. 361° F.
  • the mixed methyl-furfuryl ester of malonic acid is obtained when the reaction is not run long enough and does not go to completion.
  • the reaction temperature is allowed to go too high, there is some decomposition which gives an unsatisfactory result.
  • Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F.
  • the dimethyl esters of other lower aliphatic acids are prepared by the same transesterification reaction.
  • Dimethyl pimelate is a very high boiling liquid, b.p. 248° F. at 10 mm.
  • Dimethyl suberate is a still higher boiling liquid, b.p. 514° F.
  • Dimethyl azelate boils at 313° F. at 20 mm.
  • Dimethyl sebacate boils at 144° F. at 5 mm.
  • These esters are well known high-boiling oleagenous liquids which have had some use as synthetic lubricants.
  • the mixed methyl-furfuryl esters are obtained when the reaction is not run long enough and does not go to completion. It has also been found that when the reaction temperature is allowed to go too high, there is some decomposition and some difurfuryl esters of the lower dibasic acids are obtained.
  • the difurfuryl ester (or the mixed methyl-furfuryl esters) of the various acids are produced.
  • the difurfuryl esters and the mixed methyl furfuryl esters of the dibasic acids described above are compatible extenders for various condensation-type resins.
  • a molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl glutarate with 80% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand was then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture was added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture was formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 78 minutes at about 78° F.
  • test biscuits have a tensile strength of 196 lbs. after 24 hrs. as compared with a tensile strength of 161 lbs. for a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl glutarate ester.
  • catalysts can be used in forming the test biscuits which are customarily used in curing sand cores and molds.
  • aromatic sulfonic acids including benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, and mixtures thereof, either alone or diluted with water and/or methanol or other diluents.
  • fluoboric acid or sulfuric acid may be added.
  • a molding resin composition is prepared by mixing 35% wt. of liquid difurfuryl glutarate with 65% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 65/35 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 80 minutes at about 76° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester.
  • the tensile strength is somewhat less than in Example VI but is substantially better than the control. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl glutarate ester.
  • catalysts can be used in forming the test biscuits which are customarily used in curing sand cores and molds.
  • aromatic sulfonic acids including benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, and mixtures thereof, either alone or diluted with water and/or methanol or other diluents.
  • fluoboric acid or sulfuric acid may be added.
  • a molding resin composition is prepared by mixing 25% wt. of liquid difurfuryl glutarate with 75% wt. of a furan modified phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a toluene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 75/25 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 85 minutes at about 75° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same furan modified phenolic resin prepolymer without the difurfuryl ester.
  • the tensile strength is somewhat less than in Example VI but is substantially better than the control. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl glutarate ester.
  • test biscuits which are customarily used in curing sand cores and molds, as noted in Examples VI and VII.
  • a molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl glutarate with 80% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with about 0.5% methyl ethyl ketone peroxide as a catalyst precursor. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and peroxide and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and gassed with sulfur dioxide for about 0.5-5 seconds at a temperature of from room temperature to 85°-90° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester, and also better than a furan modified phenolic resin having about the same furfuryl content.
  • a molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl glutarate with 80% wt. of a urea-formaldehyde/furan-modified phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with about 0.6% methyl ethyl ketone peroxide as a catalyst precursor. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and peroxide and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and gassed with sulfur dioxide for about 0.5-5 seconds at a temperature of 80°-85° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same resin prepolymer without the difurfuryl ester.
  • a molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl glutarate with 80% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand was then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture was added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture was formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 78 minutes at about 78° F.
  • test biscuits have a tensile strength of 196 lbs. after 24 hrs. as compared with a tensile strength of 161 lbs. for a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl glutarate ester.
  • a molding resin composition is prepared by mixing 30% wt. of liquid difurfuryl adipate with 70% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 70/30 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 80 minutes at about 76° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl adipate ester.
  • a molding resin composition is prepared by mixing 20% wt. of liquid difurfuryl succinate with 80% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 72 minutes at about 79° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl succinate ester.
  • a molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl esters of a mixture of glutaric, succinic and adipic acids with 80% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand was then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture was added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture was formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 80 minutes at about 75° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl esters. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl mixed acid esters.
  • a molding resin composition Is prepared by mixing 25% wt. of liquid difurfuryl malonate with 75% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 75/25 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 74 minutes at about 78° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl malonate ester.
  • a molding resin composition is prepared by mixing 15% wt. of liquid difurfuryl pimelate with 85% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 85/15 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 74 minutes at about 80° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl pimelate ester.
  • a molding resin composition is prepared by mixing 20% wt. of liquid difurfuryl suberate with 80% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 70 minutes at about 82° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl suberate ester.
  • a molding resin composition is prepared by mixing 35% wt. of liquid difurfuryl azelate with 65% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 65/35 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 78 minutes at about 78° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl azelate ester.
  • a molding resin composition is prepared by mixing 20% wt. of liquid difurfuryl sebacate with 80% wt. of a phenol formaldehyde resin prepolymer.
  • a foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
  • the resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 78 minutes at about 78° F.
  • test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl sebacate ester.

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Abstract

Acid-curable, condensation-type resins, particularly phenolic resin prepolymers and urea-formaldehyde and/or furfuryl alcohol-formaldehyde modified phenolic resin prepolymers, have improved properties when admixed with a dibasic acid di-ester of the composition
R.sup.1 O.sub.2 C(CH.sub.2).sub.n CO.sub.2 R.sup.2
where n is from 1 to 8, R1 is furfuryl, and R2 is furfuryl or methyl. The di-esters are preferably added in the amount of 5-35%, by weight of total composition. These compositions are particularly useful in the preparation of sand cores and molds for foundry use which have improved strength and hardness.
The dibasic acid di-esters of the composition
R.sup.1 O.sub.2 C(CH.sub.2).sub.n CO.sub.2 R.sup.2
where n is from 1 to 8, R1 is furfuryl, and R2 is furfuryl or methyl are not reported in the literature and are novel compounds. These di-esters are oily liquids having high boiling points and are particularly useful as resin modifiers, diluents and plasticizers. These di-esters are produced by the sodium-catalyzed transesterification reaction of furfuryl alcohol with the liquid dimethyl esters of the C3 -C10 linear aliphatic dibasic acids at temperatures of about 214°-240° F.

Description

This is a continuation of application Ser. No. 503,081, filed June 14, 1983, now U.S. Pat. No. 4,481,310, issued Nov. 6, 1984, which in turn is a continuation of Ser. No. 306,965, filed Sept. 30, 1981, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to new and useful acid-curing resin compositions for use in the formation of sand cores and molds for foundry operations and to new di-esters of lower aliphatic dibasic acids.
2. Description of the Prior Art
In the foundry industry, sand is coated with resin binders and formed into molds and cores for the production of precision castings. A wide variety of techniques have been developed for the manufacture of sand cores and molds. These involve the hot box technique for mold and core formation; the shell method; the "No-Bake", and the cold-box technique.
In the hot box and shell methods, sand molds and cores are formed by heating a mixture of sand and a thermosetting resin at a temperature of about 300°-600° F. in contact with patterns which produce the desired shape for the mold or core. The resin is polymerized and a core or mold is formed. Procedures of this type are described in Dunn U.S. Pat. No. 3,059,297 and Brown U.S. pat. No. 3,020,609.
A particular disadvantage of the hot box and shell methods is the necessity for heating the pattern boxes to 300°-600° F. to polymerize and cure the resin binder. This involves considerable expense and is generally a high cost technique.
The cold box techniques for core and mold formation involve the use of sand mixed or coated with resins which may be cured at room temperature by acid or base catalysis. Acidic or basic catalysts have been used in liquid, solid or gaseous form. Typical cold box processes are shown in Blaies U.S. Pat. No. 3,008,205; Dunn U.S. Pat. No. 3,059,297; Peters U.S. Pat. No. 3,108,340; Kottke U.S. Pat. No. 3,145,438; Brown U.S. Pat. No. 3,184,814; Robins U.S. Pat. No. 3,639,654; Australian Pat. No. 453,160 and British Pat. No. 1,225,984. Many of these processes involve the use of sulfur-containing acid catalysts such as benzene sulfonic acid, toluene sulfonic acid and the like. Richard U.S. Pat. No. 3,879,339 discloses coating sand with an organic peroxide and resin, forming into a mold or core and gassing with sulfur dioxide.
A number of U.S. and foreign patents disclose the use of furfuryl alcohol and other furfuryl-substituted compounds in resin polymerization and also the use of dibasic acids and some esters in resincompositions.
Bradley U.S. Pat. No. 2,238,030 discloses the use of di-alkenyl esters of dibasic acids in the copolymerization of addition polymers.
Dannenberg U.S. Pat. No. 2,650,211 discloses polymers including dibasic acids as precursors.
Treat U.S. Pat. No. 2,999,829 discloses the copolymerization of furfuryl alcohol and maleic anhydride in the prepatatio of foundry cores.
Case U.S. Pat. No. 3,212,650 resins bases on phenol and furfuryl alcohol modified with formaldehyde and treated with an acid catalyst.
Kirkpatrick U.S. Pat. No. 3,244,770 discloses the use of di-esters of dibasic acids in phenolic resin compositions.
Bean U.S. Pat. No. 3,248,276 discloses the use of dibasic acids in resin compositions containing condensation-type resins.
Guyer U.S. Pat. No. 3,404,118 discloses the use of furfuryl glycidyl ether in molding resins.
Fitko U.S. Pat. No. 3,600,290 discloses the use of unsaturated esters in resin compositions.
Adkins U.S. Pat. No. 3,725,333 discloses the preparation of foundry molds, etc. using phenolic resins modified with furfuryl alcohol.
Laitar U.S. Pat. No. 4,051,301 discloses resins for sand cores or molds by incorporating furan into a furfuryl alcohol-modified phenolic resin prepolymer.
Anderson U.S. Pat. No. 4,083,817 discloses the acid curing of mixtures of furan-formaldehyde resins with phenolic resins for production of foundry cores and molds.
British Pat. Nos. 626,763 and 992,345 disclose the use of glyceryl esters and other esters of aliphatic dibasic acids in condensation polymers.
The bis(tetrahydrofurfuryl) ester of adipic acid is known but does not undergo condensation type polymerization.
The above noted patents, however, do not consider the problem of the preferential polymerization of furfuryl alcohol when admixed with phenolic and other condensation-type resins and the problem of short bench life, or any way to overcome these problems.
SUMMARY OF THE INVENTION
It is one object of the invention to provide a solution to some of the aforementioned problems and provide resins having a more useful bench life and produce cores and molds having greater strength and hardness.
Another object of the invention is to provide resin compositions having the properties and desires characteristics of furfuryl alcohol-containing resins without the problems of short bench life and working time.
Another object of the invention is to provide a novel class of compounds which is useful in modifying condensation-type resins.
Other objects of the invention will become apparent from time to time throughout the specification and claims as hereinafter related.
The above stated objects and other apparent objects of the invention ase accomplished by novel resin compositions comprising acid-curable, condensation-type resins, particularly phenolic resin prepolymers and urea-formaldehyde and/or furfuryl alcohol-formaldehyde modified phenolic resin prepolymers admixed with a dibasic acid di-ester of the composition
R.sup.1 O.sub.2 C(CH.sub.2).sub.n CO.sub.2 R.sup.2
where n is from 1 to 8, R1 is furfuryl, and R2 is furfuryl or methyl. The di-esters are preferably added in the amount of 5-35%, by weight of total composition. These compositions are particularly useful in the preparation of sand cores and molds for foundry use which have improved strength and hardness.
The dibasic acid di-esters of the composition
R.sup.1 O.sub.2 C(CH.sub.2).sub.n CO.sub.2 R.sup.2
where n is from 1 to 8, R1 is furfuryl, and R2 is furfuryl or methyl are not reported in the literature and are novel compounds. These di-esters are oily liquids having high boiling points and are particularly useful as resin modifiers, diluents and plasticizers. These di-esters are produced by the sodium-catalyzed transesterification reaction of furfuryl alcohol with the liquid dimethyl esters of the C3 -C10 linear aliphatic dibasic acids at temperatures of about 214°-240° F.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As noted above, the use of furfuryl alcohol modified resins in well reported in the prior art. The prior art, however, does not treat the problem of preferential polymerization of furfuryl alcohol when admixed with phenolic and other resins or suggest any solution to the problem. In this invention, it has been discovered that a novel class of esters, viz. the furfuryl-methyl esters or the difurfuryl esters of C3 -C10 linear aliphatic dibasic acids may be mixed with phenolic resin prepolymers (and other condensation-type resins) and copolymerized by acid catalysis uniformly. The use of these resin compositions in the preparation of foundry cores and molds results in easier handling of the resins and the sand-resin compositions and improved foundry cores and molds, both in tensile strength and hardness.
The preparation of the novel esters and their properties and use in resin compositions will be discussed separately below.
PREPARATION AND PROPERTIES OF FURFURYL DI-ESTERS
The difurfuryl esters and mixed methyl-furfuryl esters of aliphatic dibasic acids are prepared by a sodium-catalyzed transesterification of the corresponding dimethyl esters.
EXAMPLE I PREPARATION OF DIFURFURYL GLUTARATE
Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F. Dimethyl glutarate is a very high boiling liquid, b.p. 417° F.
196 parts by wt. of furfuryl alcohol and 160 parts by wt. dimethyl glutarate (stoichiometric proportions) were mixed and 0.5-0.75% wt. sodium metal added. The mixture was heated to a temperature in the range from 214°-240° F. under a nitrogen atmoshpere. Methanol was evolved and removed as the reaction progressed. After a period of 4 hours, a waxy solid was obtained. After washing the product with water, the residure was a liquid which was identified as difurfuryl glutarate by gas chromatography and mass spectrometric analysis.
Additional runs established that the mixed methyl-furfuryl ester of glutaric acid is obtained when the reaction is not run long enough and does not go to completion. When the reaction is carrier out with a stoichiometric excess of furfuryl alcohol, e.g. 2:1 mol ratio, the reaction goes to completion sooner but the excess furfuryl alcohol must be separated from the product. It has also been found that when the reaction temperature is allowed to go too high, there is some decomposition and an appreciable amount of difurfuryl succinate is produced.
EXAMPLE II PREPARATION OF DIFURFURYL SUCCINATE
Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F. Dimethyl succinate is a very high boiling liquid, b.p. 385° F.
196 parts by wt. of furfuryl alcohol and 146 parts by wt. dimethyl glutarate (stoichiometric proportions) were mixed and 0.5-0.75% wt. sodium metal added. The mixture was heated to a temperature in the range from 214°-240° F. under a nitrogen atmosphere. Methanol was evolved and removed as the reaction progressed. After a period of 4 hours, a waxy solid was obtained. After washing with water, a liquid residue was obtained which product was identified as difurfuryl succinate.
Additional runs established that the mixed methyl-furfuryl ester of succinic acid is obtained when the reaction is not run long enough and does not go to completion. It has also been found that when the reaction temperature is allowed to go too high, there is some decomposition and an appreciable amount of difurfuryl malonate is produced.
EXAMPLE III PREPARATION OF DIFURFURYL ADIPATE
Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F. Dimethyl adipate is a very high boiling liquid, b.p. 235° F., at 13 mm.
196 parts by wt. of furfuryl alcohol and 174 parts by wt. dimethyl adipate (stoichiometric proportions) were mixed and 0.5-0.75% wt. sodium metal added. The mixture was heated to a temperature in the range from 214°-240° F. under a nitrogen atmosphere. Methanol was evolved and removed as the reaction progressed. After a period of 4 hours, a waxy solid was obtained. After washing with water, a liquid residue was obtained which product was identified as difurfuryl adipate.
Additional runs established that the mixed methyl-furfuryl ester of adipic acid is obtained when the reaction is not run long enough and does not go to completion. It has also been found that when the reaction temperature is allowed to go too high, there is some decomposition and an appreciable amount of difurfuryl glutarate is produced.
EXAMPLE IV PREPARATION OF DIFURFURYL MALONATE
Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F. Dimethyl malonate is a very high boiling liquid, b.p. 361° F.
196 parts by wt. of furfuryl alcohol and 132 parts by wt. dimethyl malonate (stoichiometric proportions) are mixed and 0.5-0.75% wt. sodium metal added. The mixture is heated to a temperature in the range from 214°-240° F. under a nitrogen atmosphere. Methanol is evolved and removed as the reaction progressed. After a period of 4 hours, a waxy solid is obtained. The liquid product obtained after washing with water is difurfuryl malonate.
The mixed methyl-furfuryl ester of malonic acid is obtained when the reaction is not run long enough and does not go to completion. When the reaction temperature is allowed to go too high, there is some decomposition which gives an unsatisfactory result.
EXAMPLE V PREPARATION OF OTHER DIFURFURYL ESTERS
Furfuryl alcohol is a moderately high boiling liquid, b.p. 340° F. The dimethyl esters of other lower aliphatic acids are prepared by the same transesterification reaction. Dimethyl pimelate is a very high boiling liquid, b.p. 248° F. at 10 mm. Dimethyl suberate is a still higher boiling liquid, b.p. 514° F. Dimethyl azelate boils at 313° F. at 20 mm. Dimethyl sebacate boils at 144° F. at 5 mm. These esters are well known high-boiling oleagenous liquids which have had some use as synthetic lubricants.
When furfuryl alcohol and any of the above listed dimethyl esters are mixed in stoichiometric proportions and 0.5-0.75% wt. sodium metal added and the mixture heated to a temperature in the range from 214°-240° F. under a nitrogen atmosphere, the reaction proceeds as described above for the other esters. Methanol is evolved and removed as the reaction progresses. After a period of 4 hours, a waxy solid is obtained in each case. Water washing any of these products to remove impurities leaves a liquid residue which is a difurfuryl esters of the respective acids.
The mixed methyl-furfuryl esters are obtained when the reaction is not run long enough and does not go to completion. It has also been found that when the reaction temperature is allowed to go too high, there is some decomposition and some difurfuryl esters of the lower dibasic acids are obtained.
When the reaction is carried out using mixtures of the dimethyl esters of various C3 -C10 aliphatic dibasic acids in the transesterification reaction, the difurfuryl ester (or the mixed methyl-furfuryl esters) of the various acids are produced.
USES OF FURFURYL DI-ESTER/RESIN MIXTURES
The difurfuryl esters and the mixed methyl furfuryl esters of the dibasic acids described above are compatible extenders for various condensation-type resins.
PHENOLIC RESIN COMPOSITIONS WITH DIFURFURYL GLUTARATE EXAMPLE VI
A molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl glutarate with 80% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand was then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture was added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture was formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 78 minutes at about 78° F.
The test biscuits have a tensile strength of 196 lbs. after 24 hrs. as compared with a tensile strength of 161 lbs. for a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl glutarate ester.
Other catalysts can be used in forming the test biscuits which are customarily used in curing sand cores and molds. The aromatic sulfonic acids, including benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, and mixtures thereof, either alone or diluted with water and/or methanol or other diluents. Sometimes fluoboric acid or sulfuric acid may be added.
EXAMPLE VII
A molding resin composition is prepared by mixing 35% wt. of liquid difurfuryl glutarate with 65% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 65/35 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 80 minutes at about 76° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. The tensile strength is somewhat less than in Example VI but is substantially better than the control. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl glutarate ester.
When larger amounts of the ester are used, e.g. 40% and higher, the test results are poorer than the controls. Likewise, when lesser proportions of the ester are used, down to 5%, results are obtained which are better than the controls. While the range of 5-35% of the difurfuryl esters is preferred, a much wider range may be used where the desired function is that of a diluent or plasticizer in the ester/resin composition.
Other catalysts can be used in forming the test biscuits which are customarily used in curing sand cores and molds. The aromatic sulfonic acids, including benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, and mixtures thereof, either alone or diluted with water and/or methanol or other diluents. Sometimes fluoboric acid or sulfuric acid may be added.
MODIFIED RESIN COMPOSITIONS EXAMPLE VIII
A molding resin composition is prepared by mixing 25% wt. of liquid difurfuryl glutarate with 75% wt. of a furan modified phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a toluene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 75/25 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 85 minutes at about 75° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same furan modified phenolic resin prepolymer without the difurfuryl ester. The tensile strength is somewhat less than in Example VI but is substantially better than the control. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl glutarate ester.
Other catalysts can be used in forming the test biscuits which are customarily used in curing sand cores and molds, as noted in Examples VI and VII.
SULFUR DIOXIDE CURING OF RESINS CONTAINING ESTERS EXAMPLE IX
A molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl glutarate with 80% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with about 0.5% methyl ethyl ketone peroxide as a catalyst precursor. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and peroxide and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and gassed with sulfur dioxide for about 0.5-5 seconds at a temperature of from room temperature to 85°-90° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester, and also better than a furan modified phenolic resin having about the same furfuryl content.
SULFUR DIOXIDE CURING MODIFIED RESIN EXAMPLE X
A molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl glutarate with 80% wt. of a urea-formaldehyde/furan-modified phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with about 0.6% methyl ethyl ketone peroxide as a catalyst precursor. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and peroxide and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and gassed with sulfur dioxide for about 0.5-5 seconds at a temperature of 80°-85° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same resin prepolymer without the difurfuryl ester.
EXAMPLE XI
A molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl glutarate with 80% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand was then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture was added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture was formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 78 minutes at about 78° F.
The test biscuits have a tensile strength of 196 lbs. after 24 hrs. as compared with a tensile strength of 161 lbs. for a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl glutarate ester.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
RESINS CONTAINING DIFURFURYL ADIPATE EXAMPLE XII
A molding resin composition is prepared by mixing 30% wt. of liquid difurfuryl adipate with 70% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 70/30 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 80 minutes at about 76° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl adipate ester.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
RESINS CONTAINING DIFURFURYL SUCCINATE EXAMPLE XIII
A molding resin composition is prepared by mixing 20% wt. of liquid difurfuryl succinate with 80% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 72 minutes at about 79° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl succinate ester.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
RESINS CONTAINING MIXED DIFURFURYL ESTERS EXAMPLE XIV
A molding resin composition was prepared by mixing 20% wt. of liquid difurfuryl esters of a mixture of glutaric, succinic and adipic acids with 80% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand was then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture was added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture was formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 80 minutes at about 75° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl esters. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl mixed acid esters.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
RESINS CONTAINING DIFURFURYL MALONATE EXAMPLE XV
A molding resin composition Is prepared by mixing 25% wt. of liquid difurfuryl malonate with 75% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 75/25 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 74 minutes at about 78° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl malonate ester.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
RESINS CONTAINING DIFURFURYL PIMELATE EXAMPLE XVI
A molding resin composition is prepared by mixing 15% wt. of liquid difurfuryl pimelate with 85% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 85/15 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 74 minutes at about 80° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl pimelate ester.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
RESINS CONTAINING DIFURFURYL SUBERATE EXAMPLE XVII
A molding resin composition is prepared by mixing 20% wt. of liquid difurfuryl suberate with 80% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 70 minutes at about 82° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl suberate ester.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
RESINS CONTAININE DIFURFURYL AZELATE EXAMPLE XVIII
A molding resin composition is prepared by mixing 35% wt. of liquid difurfuryl azelate with 65% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 65/35 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 78 minutes at about 78° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl azelate ester.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
RESINS CONTAINING DIFURFURYL SEBACATE EXAMPLE XIX
A molding resin composition is prepared by mixing 20% wt. of liquid difurfuryl sebacate with 80% wt. of a phenol formaldehyde resin prepolymer.
A foundry-grade sand is then mixed with a benzene sulfonic acid catalyst in the amount of 45% by weight of the resin composition to be added. Then, 1.25%, by weight of the sand, of 80/20 resin-ester mixture is added to the sand and catalyst and thoroughly mixed.
The resin composition-sand mixture is formed into test biscuits, simulating a foundry core or mold, and allowed to cure for 78 minutes at about 78° F.
The test biscuits have a tensile strengths after 24 hrs. which are better than the tensile strength of a control produced under the same conditions using the same phenolic resin prepolymer without the difurfuryl ester. Substantially the same results are obtained using slightly greater amounts of the mixed methyl-furfuryl sebacate ester.
Other catalysts may be used with this resin composition, particularly those discussed in Examples VI and VII, above.
While this invention has been described fully and completely with special emphasis upon several preferred embodiments, it should be understood that within the scope of the appended claims this invention may be practiced otherwise than as specifically described herein.

Claims (10)

I claim:
1. A dibasic acid di-ester of the composition
R.sup.1 O.sub.2 C(CH.sub.2).sub.n CO.sub.2 R.sup.2
where n is from 1 to 8, R1 is furfuryl, and R2 is furfuryl or methyl.
2. A dibasic acid di-ester according to claim 1 consisting essentially of a di-furfuryl ester or a mixed furfuryl-methyl di-ester of glutaric acid.
3. A dibasic acid di-ester according to claim 1 consisting essentially of a di-furfuryl ester or a mixed furfuryl-methyl di-ester of succinic acid.
4. A dibasic acid di-ester according to claim 1 consisting essentially of a di-furfuryl ester or a mixed furfuryl-methyl di-ester of malonic acid.
5. A dibasic acid di-ester according to claim 1 consisting essentially of a di-furfuryl ester or a mixed furfuryl-methyl di-ester of adipic acid.
6. A dibasic acid di-ester according to claim 1 consisting essentially of a di-furfuryl ester or a mixed furfuryl-methyl di-ester of pimelic acid.
7. A dibasic acid di-ester according to claim 1 consisting essentially of a di-furfuryl ester or a mixed furfuryl-methyl di-ester of suberic acid.
8. A dibasic acid di-ester according to claim 1 consisting essentially of a di-furfuryl ester or a mixed furfuryl-methyl di-ester of azelaic acid.
9. A dibasic acid di-ester according to claim 1 consisting essentially of a di-furfuryl ester or a mixed furfuryl-methyl di-ester of sebacic acid.
10. A mixture of dibasic acid di-esters according to claim 1 in which n is a plurality of numbers from 1 to 8.
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Publication number Priority date Publication date Assignee Title
WO2014093624A1 (en) * 2012-12-13 2014-06-19 Polyone Corporation Furfuryl-based esters
US20180126449A1 (en) * 2015-04-14 2018-05-10 Huttenes Albertus France Phenolic resin composition for use in the polyurethane cold-box and/or no-bake process and corresponding two-component binder systems, uses, and processes

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Publication number Priority date Publication date Assignee Title
WO2014093624A1 (en) * 2012-12-13 2014-06-19 Polyone Corporation Furfuryl-based esters
US20180126449A1 (en) * 2015-04-14 2018-05-10 Huttenes Albertus France Phenolic resin composition for use in the polyurethane cold-box and/or no-bake process and corresponding two-component binder systems, uses, and processes
US10835949B2 (en) * 2015-04-14 2020-11-17 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Phenolic resin composition for use in the polyurethane cold-box and/or no-bake process and corresponding two-component binder systems, uses, and processes

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